Method for Producing Monoamino-Functionalised Dialkylphosphinite Acids Esters and Salts and Use Thereof

ABSTRACT

The invention relates to method for producing mono amino-functionalised dialkylphosphonic acids esters and salts, characterised in that a) a phosphinic acid source (I) is reacted with olefins (IV) in the presence of a catalyst A to give an alkylphosphonous acid, the salt or ester thereof (II), b) the alkylphosphonous acid, the salt or ester thereof (II) produced above is reacted with an allylamine of formula (V) in the presence of a catalyst B to give mono amino-functionalised dialkylphosphinic acid derivatives (III) where, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9  independently=amongst others, H, C 1 -C 18  alkyl, C 6 -C 18  aryl, C 6 -C 18  aralkyl, C 6 -C 18  alkylaryl and X═H, C 1 -C 18  alkyl, C 6 -C 18  aryl, C 6 -C 18  aralkyl, C 6 -C 18  alkylaryl, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li, Na, K and/or a protonated nitrogen base and Y=a mineral acid, a carboxylic acid, a Lewis acid or organic acid, where n=a whole or fractional number from 0 to 4, catalyst A is a transition metal and/or transition metal compound and/or catalyst system comprising a transition metal and/or a transition metal compound and at least one ligand and catalyst B is compounds forming peroxides and/or peroxide compounds and/or azo compounds.

This invention relates to a method for producingmonoamino-functionalized dialkylphosphinic acids, esters and salts andto their use.

Hitherto there are no methods in existence for producingmonoamino-functionalized dialkylphosphinic acids, esters and salts thatare available economically and on a large industrial scale and moreparticularly enable a high space-time yield to be achieved. Nor arethere any methods that are sufficiently effective without unwelcomehalogen compounds as starting materials, nor any where the end productsare easy to obtain or isolate or else obtainable in a specific anddesirable manner under controlled reaction conditions (such as atransesterification for example).

The invention accordingly provides a method for, producingmonoamino-functionalized dialkylphosphinic acids, esters and salts,which comprises

a) reacting a phosphinic acid source (I)

with olefins (IV)

in the presence of a catalyst A to form an alkylphosphonous acid, saltor ester (II)

b) reacting the resulting alkylphosphonous acid, salt or ester (II) withan allyl-amine (V)

in the presence of a catalyst B to form the monoamino-functionalizeddialkylphosphinic acid derivative (III)

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ are identical or different andare each independently H, C₁-C₁₈-alkyl, C₆-C₁₈-aryl, C₆-C₁₈-aralkyl,C₆-C₁₈-alkylaryl, CN, CHO, OC(O)CH₂CN, CH(OH)C₂H₅, CH₂CH(OH)CH₃,9-anthracene, 2-pyrrolidone, (CH₂)_(m)OH, (CH₂)_(m)NH₂, (CH₂)_(m)NCS,(CH₂)_(m)NC(S)NH₂, (CH₂)_(m)SH, (CH₂)_(m)S-2-thiazoline, (CH₂)_(m)SiMe₃,C(O)R¹⁰, (CH₂)_(m)C(O)R¹⁰, CH═CHR¹⁰ and/or CH═CH—C(O)R¹⁰ and where R¹⁰is C₁-C₈-alkyl or C₆-C₁₈-aryl and m is an integer from 0 to 10 and X isC₁-C₁₈-alkyl, C₆-C₁₈-aryl, C₆-C₁₈-aralkyl, C₆-C₁₈-alkylaryl,(CH₂)_(k)OH, CH₂—CHOH—CH₂OH, (CH₂)_(k)O(CH₂)_(k)H,(CH₂)_(k)—CH(OH)—(CH₂)_(k)H, (CH₂—CH₂O)_(k)H, (CH₂—C[CH₃]HO)_(k)H,(CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)H, (CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)H,(CH₂—CH₂O)_(k)-alkyl, (CH₂—C[CH₃]HO)_(k)-alkyl,(CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)-alkyl,(CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)O-alkyl, (CH₂)_(k)—CH═CH(CH₂)_(k)H,(CH₂)_(k)NH₂, (CH₂)_(k)N[(CH₂)_(k)H]₂, where k is an integer from 0 to10, and/or Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu,Ni, Li, Na, K, H and/or a protonated nitrogen base and is a mineralacid, carboxylic acid, Lewis acid or organic acid, where n is a whole orfractional number from 0 to 4 and the catalyst A comprises transitionmetals and/or transition metal compounds and/or catalyst systemscomposed of a transition metal and/or transition metal compound and atleast one ligand, and the catalyst B comprises peroxide-formingcompounds and/or peroxo compounds and/or azo compounds.

Preferably, the monoamino-functionalized dialkylphosphinic acid, itssalt or ester (III) obtained after step b) is subsequently reacted in astep c) with metal compounds of Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn,Ce, Bi, Sr, Mn Li, Na, K and/or a protonated nitrogen base to form thecorresponding monoamino-functionalized dialkylphosphinic acid salts(III) of these metals and/or of a nitrogen compound.

Preferably, the alkylphosphonous acid, salt or ester (II) obtained afterstep a) and/or the monoamino-functionalized dialkylphosphinic acid, saltor ester (III) obtained after step b) and/or the particular resultingreaction solution thereof are esterified with an alkylene oxide or analcohol M-OH and/or M′-OH, and the respectively resultingalkylphosphonous ester (II) and/or monoamino-functionalizeddialkylphosphinic ester (III) are subjected to the further reactionsteps b) or c).

Preferably, the groups C₆-C₁₈-aryl, C₆-C₁₈-aralkyl and C₆-C₁₈-alkylarylare substituted with SO₃X₂, —C(O)CH₃, OH, CH₂OH, CH₃SO₃X₂, PO₃X₂, NH₂,NO₂, OCH₃, SH and/or OC(O)CH₃.

Preferably, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ are identical ordifferent and are each independently H, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl and/or phenyl.

Preferably, X is H, Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol,propyl glycol, butyl glycol, pentyl glycol, hexyl glycol, allyl and/orglycerol.

Preferably m=1 to 10 and k=2 to 10.

Preferably, Y is hydrochloric acid, sulfuric acid, nitric acid orphosphoric acid, phosphonic acid, phosphinic acid, formic acid, aceticacid, propionic acid, butyric acid, lactic acid, palmitic acid, stearicacid, malonic acid, maleic acid, fumaric acid, tartaric acid, citricacid, ascorbic acid, trimethylborane, triethylborane, tributylborane ortriphenylborane.

Preferably n is 0, ¼, ⅓, ½, 1, 2, 3 and 4.

Preferably, the catalyst systems A are each formed by reaction of atransition metal and/or of a transition metal compound and at least oneligand.

Preferably, the transition metals and/or transition metal compoundscomprise such from the seventh and eighth transition groups.

Preferably, the transition metals and/or transition metal compoundscomprise rhodium, ruthenium, nickel, palladium, platinum.

Preferably, the catalyst B comprises hydrogen peroxide, sodium peroxide,lithium peroxide, potassium persulfate, sodium persulfate, ammoniumpersulfate, sodium peroxodisulfate, potassium peroxoborate, peraceticacid, benzoyl peroxide, di-t-butyl peroxide and/or peroxodisulfuric acidand/or comprises azodiisobutyronitrile,2,2′-azobis(2-amidinopropane)dihydrochloride and/or2,2′-azobis(N,N′-dimethyleneisobutyramidine)dihydrochloride.

Preferably, the allylamines (V) comprise allylamine, N-methylallylamine,N,N-dimethylallylamine, N-(trimethylsilyl)allylamine, N-allylaniline,N-methyl-N-allylaniline, N-methylallylaniline, 1,1-dimethylallylamine,2-methylallylamine, 3-phenylallylamine, allylcyclohexylamine,diallylamine, diallylmethylamine, triallylamine and/or their salts withmineral acids, carboxylic acids, Lewis acids, organic acids or mixturesthereof.

Preferably, the alcohol of the general formula M-OH comprises linear orbranched, saturated and unsaturated, monohydric organic alcohols havinga carbon chain length of C₁-C₁₈ and the alcohol of the general formulaM′-OH comprises linear or branched, saturated and unsaturated polyhydricorganic alcohols having a carbon chain length of C₁-C₁₈.

The present invention also provides for the use ofmonoamino-functionalized dialkylphosphinic acids, esters and saltsobtained according to one or more of claims 1 to 11 as an intermediatefor further syntheses, as a binder, as a crosslinker or accelerant tocure epoxy resins, polyurethanes and unsaturated polyester resins, aspolymer stabilizers, as crop protection agents, as a therapeutic oradditive in therapeutics for humans and animals, as a sequestrant, as amineral oil additive, as a corrosion control agent, in washing andcleaning applications and in electronic applications.

The present invention also provides for the use ofmonoamino-functionalized dialkylphosphinic acids, salts and estersobtained according to one or more of claims 1 to 11 as a flameretardant, more particularly as a flame retardant for clearcoats andintumescent coatings, as a flame retardant for wood and other cellulosicproducts, as a reactive and/or nonreactive flame retardant for polymers,in the manufacture of flame-retardant polymeric molding materials, inthe manufacture of flame-retardant polymeric molded articles and/or forflame-retardant finishing of polyester and cellulose straight and blendfabrics by impregnation.

The present invention also provides a flame-retardant thermoplastic orthermoset polymeric molding material containing 0.5% to 45% by weight ofmonoamino-functionalized dialkylphosphinic acids, salts or estersobtained according to one or more of claims 1 to 11, 0.5% to 95% byweight of thermoplastic or thermoset polymer or mixtures thereof, 0% to55% by weight of additives and 0% to 55% by weight of filler orreinforcing materials, wherein the sum total of the components is 100%by weight.

Lastly, the invention also provides flame-retardant thermoplastic orthermoset polymeric molded articles, films, threads and fiberscontaining 0.5% to 45% by weight of monoamino-functionalizeddialkylphosphinic acids, salts or esters (III) obtained according to oneor more of claims 1 to 12, 0.5% to 95% by weight of thermoplastic orthermoset polymer or mixtures thereof, 0% to 55% by weight of additivesand 0% to 55% by weight of filler or reinforcing materials, wherein thesum total of the components is 100% by weight.

All the aforementioned reactions can also be carried out in stages;similarly, the various processing steps can also utilize the respectiveresulting reaction solutions.

When the monoamino-functionalized dialkylphosphinic acid (III) afterstep c) comprises an ester, an acidic or basic hydrolysis may preferablybe carried out in order that the free monoamino-functionalizeddialkylphosphinic acid or salt may be obtained.

Preferably, the target compounds to be produced, i.e. themonoamino-functionalized dialkylphosphinic acids comprise3-(ethylhydroxyphosphinyl)-1-aminopropane,3-(propylhydroxyphosphinyl)-1-aminopropane,3-(i-propylhydroxyl-phosphinyl)-1-aminopropane,3-(butylhydroxyphosphinyl)-1-aminopropane,3-(sec-butylhydroxyphosphinyl)-1-aminopropane,3-(i-butylhydroxyphosphinyl)-1-aminopropane,3-(2-phenylethylhydroxyphosphinyl)-1-aminopropane,3-(ethylhydroxyphosphinyl)-2-methyl-1-aminopropane,3-(propylhydroxyphosphinyl)-2-methyl-1-aminopropane,3-(i-propylhydroxyphosphinyl)-2-methyl-1-aminopropane,3-(butylhydroxyphosphinyl)-2-methyl-1-aminopropane,3-(sec-butylhydroxyphosphinyl)-2-methyl-1-aminopropane,3-(i-butylhydroxyphosphinyl)-2-methyl-1-aminopropane,3-(2-phenylethylhydroxyphosphinyl)-2-methyl-1-aminopropane,3-(ethylhydroxyphosphinyl)-3-phenyl-1-aminopropane,3-(propylhydroxyphosphinyl)-3-phenyl-1-aminopropane,3-(i-propylhydroxyphosphinyl)-3-phenyl-1-aminopropane,3-(butylhydroxyphosphinyl)-3-phenyl-1-aminopropane,3-(sec-butylhydroxyphosphinyl)-3-phenyl-1-aminopropane,3-(i-butylhydroxyphosphinyl)-3-phenyl-1-aminopropane,3-(2-phenylethylhydroxyphosphinyl)-3-phenyl-1-aminopropane; the esterscomprise methyl, ethyl; i-propyl; butyl, phenyl; 2-hydroxyethyl,2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl and/or2,3-dihydroxypropyl ester of the aforementioned monoamino-functionalizeddialkylphosphinic acids and the salts comprise an aluminum(III),calcium(II), magnesium(II), cerium(III), titanium(IV) and/or zinc(II)salt of the aforementioned monoamino-functionalized dialkylphosphinicacids.

Preferably, the amino functionality of the abovementionedmonoamino-functionalized dialkylphosphinic acids, their salts and estersof the formula (III) is a “free” amine or combines with mineral acids,carboxylic acids, Lewis acids, organic acids or mixtures thereof to formammonium salts.

Preferred mineral acids are for example hydrochloric acid, sulfuricacid, nitric acid or phosphoric acid, phosphonic acid, phosphinic acid.

Preferred carboxylic acids are for example formic acid, acetic acid,propionic acid, butyric acid, lactic acid, palmitic acid, stearic acid,masonic acid, maleic acid, fumaric acid, tartaric acid, citric acid andascorbic acid.

Preferred Lewis acids are boranes, for example diborane,trialkylboranes, for example trimethylborane, triethylborane,tributylborane and triarylboranes, for example triphenylborane.

Preferably, the transition metals for catalyst A comprise elements ofthe seventh and eighth transition groups (a metal of group 7, 8, 9 or10, in modern nomenclature), for example rhenium, ruthenium, cobalt,rhodium, iridium, nickel, palladium and platinum.

Preference for use as source of the transition metals and transitionmetal compounds is given to their metal salts. Suitable salts are thoseof mineral acids containing the anions fluoride, chloride, bromide,iodide, fluorate, chlorate, bromate, iodate, fluorite, chlorite,bromite, iodite, hypofluorite, hypochlorite, hypobromite, hypoiodite,perfluorate, perchlorate, perbromate, periodate, cyanide, cyanate,nitrate, nitride, nitrite, oxide, hydroxide, borate, sulfate, sulfite,sulfide, persulfate, thiosulfate, sulfamate, phosphate, phosphite,hypophosphite, phosphide, carbonate and sulfonate, for examplemethanesulfonate, chloro-sulfonate, fluorosulfonate,trifluoromethanesulfonate, benzenesulfonate, naphthylsulfonate,toluenesulfonate, t-butylsulfonate, 2-hydroxypropanesulfonate andsulfonated ion exchange resins; and/or organic salts, for exampleacetylacetonates and salts of a carboxylic acid having up to 20 carbonatoms, for example formate, acetate, propionate, butyrate, oxalate,stearate and citrate including halogenated carboxylic acids having up to20 carbon atoms, for example trifluoroacetate, trichloroacetate.

A further source of the transition metals and transition metal compoundsis salts of the transition metals with tetraphenylborate and halogenatedtetraphenylborate anions, for example perfluorophenylborate.

Suitable salts similarly include double salts and complex saltsconsisting of one or more transition metal ions and independently one ormore alkali metal, alkaline earth metal, ammonium, organic ammonium,phosphonium and organic phosphonium ions and independently one or moreof the abovementioned anions. Examples of suitable double salts areammonium hexachloropalladate and ammonium tetrachloropalladate.

Preference for use as a source of the transition metals is given to thetransition metal as an element and/or a transition metal compound in itszerovalent state.

Preferably, the transition metal salt is used as a metal, or as an alloywith further metals, in which case boron, zirconium, tantalum, tungsten,rhenium, cobalt, iridium, nickel, palladium, platinum and/or gold ispreferred here. The transition metal content in the alloy used ispreferably 45-99.95% by weight.

Preferably, the transition metal is used in microdisperse form (particlesize 0.1 mm-100 μm).

Preferably, the transition metal is used supported on a metal oxide suchas, for example, alumina, silica, titanium dioxide, zirconium dioxide,zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesiumoxide, Celite®, diatomaceous earth, on a metal carbonate such as, forexample, barium carbonate, calcium carbonate, strontium carbonate, on ametal sulfate such as, for example, barium sulfate, calcium sulfate,strontium sulfate, on a metal phosphate such as, for example, aluminumphosphate, vanadium phosphate, on a metal carbide such as, for example,silicone carbide, on a metal aluminate such as, for example, calciumaluminate, on a metal silicate such as for example, aluminum silicate,chalks, zeolites, bentonite, montmorillonite, hectorite, onfunctionalized silicates, functionalized silica gels such as, forexample, SiliaBond®, QuadraSil™, on functionalized polysiloxanes suchas, for example, Deloxan®, on a metal nitride, on carbon, activatedcarbon, mullite, bauxite, antimonite, scheelite, perovskite,hydrotalcite, heteropolyanions, on functionalized and unfunctionalizedcellulose, chitosan, keratin, heteropolyanions, on ion exchangers suchas, for example, Amberlite™, Amberjet™, Ambersep™, Dowex®, Lewatit®,ScavNet®, on functionalized polymers such as, for example, Chelex®,QuadraPure™, Smopex®, PolyOrgs®, on polymer-bound phosphanes, phosphaneoxides, phosphinates, phosphonates, phosphates, amines, ammonium salts,amides, thioamides, ureas, thioureas, triazines, imidazoles, pyrazoles,pyridines, pyrimidines, pyrazines, thiols, thiol ethers, thiol esters,alcohols, alkoxides, ethers, esters, carboxylic acids, acetates,acetals, peptides, hetarenes, polyethyleneimine/silica and/ordendrimers.

Suitable sources for the metal salts and/or transition metals likewisepreferably include their complex compounds. Complex compounds of themetal salts and/or transition metals are composed of the metalsalts/transition metals and one or more complexing agents. Suitablecomplexing agents include for example olefins, diolefins, nitriles,dinitriles, carbon monoxide, phosphines, diphosphines, phosphites,diphosphites, dibenzylideneacetone, cyclopentadienyl, indenyl orstyrene. Suitable complex compounds of the metal salts and/or transitionmetals may be supported on the abovementioned support materials.

The proportion in which the supported transition metals mentioned arepresent is preferably in the range from 0.01% to 20% by weight, morepreferably from 0.1% to 10% by weight and even more preferably from 0.2%to 5% by weight, based on the total mass of the support material.

Suitable sources for transition metals and transition metal compoundsinclude for example palladium, platinum, nickel, rhodium; palladiumplatinum, nickel or rhodium, on alumina, on silica, on barium carbonate,on barium sulfate, on calcium carbonate, on strontium carbonate, oncarbon, on activated carbon; platinum-palladium-gold alloy,aluminum-nickel alloy, iron-nickel alloy, lanthanide-nickel alloy,zirconium-nickel alloy, platinum-iridium alloy, platinum-rhodium alloy;Raney® nickel, nickel-zinc-iron oxide; palladium(II) chloride,palladium(II) bromide, palladium(II) iodide, palladium(II) fluoride,palladium(II) hydride, palladium(II) oxide, palladium(II) peroxide,palladium(II) cyanide, palladium(II) sulfate, palladium(II) nitrate,palladium(II) phosphide, palladium(II) boride, palladium(II) chromiumoxide, palladium(II) cobalt oxide, palladium(II) carbonate hydroxide,palladium(II) cyclohexane butyrate, palladium(II) hydroxide,palladium(II) molybdate, palladium(II) octanoate, palladium(II) oxalate,palladium(II) perchlorate, palladium(II) phthalocyanine, palladium(II)5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, palladium(II)sulfamate, palladium(II) perchlorate, palladium(II) thiocyanate,palladium(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), palladium(II)propionate, palladium(II) acetate, palladium(II) stearate, palladium(II)2-ethylhexanoate, palladium(II) acetylacetonate, palladium(II)hexafluoroacetylacetonate, palladium(II) tetrafluoroborate,palladium(II) thiosulfate, palladium(II) trifluoroacetate, palladium(II)phthalocyaninetetrasulfonic acid tetrasodium salt, palladium(II) methyl,palladium(II) cyclopentadienyl, palladium(II) methylcyclopentadienyl,palladium(II) ethylcyclopentadienyl, palladium(II)pentamethylcyclopentadienyl, palladium(II)2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, palladium(II)5,10,15,20-tetraphenyl-21H,23H-porphine,bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), palladium(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, palladium(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, palladium(II)5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;

nickel(II) chloride, nickel(II) bromide, nickel(II) iodide, nickel(II)fluoride, nickel(II) hydride, nickel(II) oxide, nickel(II) peroxide,nickel(II) cyanide, nickel(II) sulfate, nickel(II) nitrate, nickel(II)phosphide, nickel(II) boride, nickel(II) chromium oxide, nickel(II)cobalt oxide, nickel(II) carbonate hydroxide, nickel(II) cyclohexanebutyrate, nickel(II) hydroxide, nickel(II) molybdate, nickel(II)octanoate, nickel(II) oxalate, nickel(II) perchlorate, nickel(II)phthalocyanine, nickel(II)5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, nickel(II)sulfamate, nickel(II) perchlorate, nickel(II) thiocyanate, nickel(II)bis(2,2,6,6-tetramethyl-3,5-heptanedionate), nickel(II) propionate,nickel(II) acetate, nickel(II) stearate, nickel(II) 2-ethylhexanoate,nickel(II) acetylacetonate, nickel(II) hexafluoroacetylacetonate,nickel(II) tetrafluoroborate, nickel(II) thiosulfate, nickel(II)trifluoroacetate, nickel(II) phthalocyaninetetrasulfonic acidtetrasodium salt, nickel(II) methyl, nickel(II) cyclopentadienyl,nickel(II) methylcyclopentadienyl, nickel(II) ethylcyclopentadienyl,nickel(II) pentamethylcyclopentadienyl, nickel(II)2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, nickel(II)5,10,15,20-tetraphenyl-21H,23H-porphine, nickel(II)bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), nickel(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, nickel(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, nickel(II)5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;

platinum(II) chloride, platinum(II) bromide, platinum(II) iodide,platinum(II) fluoride, platinum(II) hydride, platinum(II) oxide,platinum(II) peroxide, platinum(II) cyanide, platinum(II) sulfate,platinum(II) nitrate, platinum(II) phosphide, platinum(II) boride,platinum(II) chromium oxide, platinum(II) cobalt oxide, platinum(II)carbonate hydroxide, platinum(II) cyclohexane butyrate, platinum(II)hydroxide, platinum(II) molybdate, platinum(II) octanoate, platinum(II)oxalate, platinum(II) perchlorate, platinum(II) phthalocyanine,platinum(II) 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine,platinum(II) sulfamate, platinum(II) perchlorate, platinum(II)thiocyanate, platinum(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate),platinum(II) propionate, platinum(II) acetate, platinum(II) stearate,platinum(II) 2-ethylhexanoate, platinum(II) acetylacetonate,platinum(II) hexafluoroacetylacetonate, platinum(II) tetrafluoroborate,platinum(II) thiosulfate, platinum(II) trifluoroacetate, platinum(II)phthalocyaninetetrasulfonic acid tetrasodium salt, platinum(II) methyl,platinum(II) cyclopentadienyl, platinum(II) methylcyclopentadienyl,platinum(II) ethylcyclopentadienyl, platinum(II)pentamethylcyclopentadienyl, platinum(II)2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, platinum(II)5,10,15,20-tetraphenyl-21H,23H-porphine, platinum(II)bis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), platinum(II)2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, platinum(II)2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, platinum(II)5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenyl-sulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylamino-methyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis-(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;

rhodium chloride, rhodium bromide, rhodium iodide, rhodium fluoride,rhodium hydride, rhodium oxide, rhodium peroxide, rhodium cyanide,rhodium sulfate, rhodium nitrate, rhodium phosphide, rhodium boride,rhodium chromium oxide, rhodium cobalt oxide, rhodium carbonatehydroxide, rhodium cyclohexane butyrate, rhodium hydroxide, rhodiummolybdate, rhodium octanoate, rhodium oxalate, rhodium perchlorate,rhodium phthalocyanine, rhodium5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, rhodiumsulfamate, rhodium perchlorate, rhodium thiocyanate, rhodiumbis(2,2,6,6-tetramethyl-3,5-heptanedionate), rhodium propionate, rhodiumacetate, rhodium stearate, rhodium 2-ethylhexanoate, rhodiumacetylacetonate, rhodium hexafluoroacetylacetonate, rhodiumtetrafluoroborate, rhodium thiosulfate, rhodium trifluoroacetate,rhodium phthalocyaninetetrasulfonic acid tetrasodium salt, rhodiummethyl, rhodium cyclopentadienyl, rhodium methylcyclopentadienyl,rhodium ethylcyclopentadienyl, rhodium pentamethylcyclopentadienyl,rhodium 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphine, rhodium5,10,15,20-tetraphenyl-21H,23H-porphine, rhodiumbis(5-[[4-(dimethylamino)phenyl]imino]-8(5H)-quinolinone), rhodium2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine, rhodium2,9,16,23-tetraphenoxy-29H,31H-phthalocyanine, rhodium5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphine and the1,4-bis(diphenylphosphine)butane, 1,3-bis(diphenylphosphino)propane,2-(2′-di-tert-butylphosphine)biphenyl, acetonitrile, benzonitrile,ethylenediamine, chloroform, 1,2-bis(phenylsulfinyl)ethane,1,3-bis(2,6-diisopropylphenyl)imidazolidene)(3-chloropyridyl),2′-(dimethylamino)-2-biphenylyl, dinorbornylphosphine,2-(dimethylaminomethyl)ferrocene, allyl, bis(diphenylphosphino)butane,(N-succinimidyl)bis(triphenylphosphine), dimethylphenylphosphine,methyldiphenylphosphine, 1,10-phenanthroline, 1,5-cyclooctadiene,N,N,N′,N′-tetramethylethylenediamine, triphenylphosphine,tri-o-tolylphosphine, tricyclohexylphosphine, tributylphosphine,triethylphosphine, 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene,1,3-bis(mesityl)imidazol-2-ylidene,1,1′-bis(diphenylphosphino)ferrocene, 1,2-bis(diphenylphosphino)ethane,N-methylimidazole, 2,2′-bipyridine, (bicyclo[2.2.1]hepta-2,5-diene),bis(di-tert-butyl(4-dimethylaminophenyl)phosphine), bis(tert-butylisocyanide), 2-methoxyethyl ether, ethylene glycol dimethyl ether,1,2-dimethoxyethane, bis(1,3-diamino-2-propanol),bis(N,N-diethylethylenediamine), 1,2-diaminocyclohexane, pyridine,2,2′:6′,2″-terpyridine, diethyl sulfide, ethylene and amine complexesthereof;

potassium hexachloropalladate(IV), sodium hexachloropalladate(IV),ammonium hexachloropalladate(IV), potassium tetrachloropalladate(II),sodium tetrachloropalladate(II), ammonium tetrachloropalladate(II),bromo(tri-tert-butylphosphine)palladium(I) dimer,(2-methylallyl)palladium(II) chloride dimer,bis(dibenzylideneacetone)palladium(0),tris(dibenzylideneacetone)dipalladium(0),tetrakis(triphenylphosphine)palladium(0),tetrakis(tricyclohexylphosphine)palladium(0),bis[1,2-bis(diphenylphosphine)ethane]palladium(0),bis(3,5,3′,5′-dimethoxydibenzylideneacetone)palladium(0),bis(tri-tert-butylphosphine)-palladium(0),meso-tetraphenyltetrabenzoporphinepalladium,tetrakis(methyldiphenylphosphine)palladium(0),tris(3,3′,3″-phophinidyne-tris(benzenesulfonato)palladium(0) nonasodiumsalt,1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0),1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene(1,4-naphthoquinone)palladium(0)and the chloroform complex thereof;

allylnickel(II) chloride dimer, ammoniumnickel(II) sulfate,bis(1,5-cyclooctadiene)nickel(0),bis(triphenylphosphine)dicarbonylnickel(0),tetrakis(triphenylphosphine)nickel(0), tetrakis(triphenylphosphite)nickel(0), potassium hexafluoronickelate(IV), potassiumtetracyanonickelate(II), potassium nickel(IV) paraperiodate, dilithiumtetrabromonickelate(II), potassium tetracyanonickelate(II); platinum(IV)chloride, platinum(IV) oxide, platinum(IV) sulfide, potassiumhexachloroplatinate(IV), sodium hexachloroplatinate(IV), ammoniumhexachloroplatinate(IV), potassium tetrachloroplatinate(I), ammoniumtetrachloroplatinate(II), potassium tetracyanoplatinate(II)trimethyl(methylcyclopentadienyl)platinum(IV),cis-diammintetrachloroplatinum(IV), potassiumtrichloro(ethylene)platinate(II), sodium hexahydroxyplatinate(IV),tetraamineplatinum(II) tetrachloroplatinate(II), tetrabutylammoniumhexachloroplatinate(IV), ethylenebis(triphenylphosphine)platinum(0),platinum(0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, platinum(0)2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane,tetrakis(triphenylphosphine)platinum(0), platinum octaethylporphyrine,chloroplatinic acid, carboplatin; chlorobis(ethylene)rhodium dimer,hexarhodium hexadecacarbonyl, chloro(1,5-cyclooctadiene)rhodium dimer,chloro(norbomadiene)rhodium dimer, chloro(1,5-hexadiene)rhodium dimer.

The ligands preferably comprise phosphines of the formula (VI)

PR¹¹ ₃   (VI)

where the R¹¹ radicals are each independently hydrogen, straight-chain,branched or cyclic C₁-C₂₀-alkyl, C₁-C₂₀-alkylaryl, C₂-C₂₀-alkenyl,C₂-C₂₀-alkynyl, C₁-C₂₀-carboxylate, C₁-C₂₀-alkoxy, C₁-C₂₀-alkenyloxy,C₁-C₂₀-alkynyloxy, C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio,C₁-C₂₀-alkylsulfonyl, C₁-C₂₀-alkylsulfinyl, silyl and/or theirderivatives and/or phenyl substituted by at least one R¹², or naphthylsubstituted by at least one R¹². R¹² in each occurrence is independentlyhydrogen, fluorine, chlorine, bromine, iodine, NH₂, nitro, hydroxyl,cyano, formyl, straight-chain, branched or cyclic C₁-C₂₀-alkyl,C₁-C₂₀-alkoxy, HN(C₁-C₂₀-alkyl), N(C₁-C₂₀-alkyl)₂, —CO₂—(C₁-C₂₀-alkyl),—CON(C₁-C₂₀-alkyl)₂, —OCO(C₁-C₂₀-alkyl), NHCO(C₁-C₂₀-alkyl),C₁-C₂₀-Acyl, —SO₃M, —SO₂N(R¹³)M, —CO₂M, —PO₃M₂, —AsO₃M₂, —SiO₂M,—C(CF₃)₂OM (M=H, Li, Na or K), where R¹³ is hydrogen, fluorine,chlorine, bromine, iodine, straight-chain, branched or cyclicC₁-C₂₀-alkyl, C₂-C₂₀-alkenyl, C₂-C₂₀-alkynyl, C₁-C₂₀-carboxylate,C₁-C₂₀-alkoxy, C₁-C₂₀-alkenyloxy, C₁-C₂₀-alkynyloxy,C₂-C₂₀-alkoxycarbonyl, C₁-C₂₀-alkylthio, C₁-C₂₀-alkylsulfonyl,C₁-C₂₀-alkylsulfinyl, silyl and/or their derivatives, aryl,C₁-C₂₀-arylalkyl, C₁-C₂₀-alkylaryl, phenyl and/or biphenyl. Preferably,the R¹¹ groups are all identical.

Suitable phosphines(VI) are for example trimethylphosphine,triethylphosphine, tripropylphosphine, triisopropylphosphine,tributylphosphine, triisobutylphosphine, triisopentylphosphine,trihexylphosphine, tricyclohexylphosphine, trioctylphosphine,tridecylphosphine, triphenylphosphine, diphenylmethylphosphine,phenyldimethylphosphine, tri(o-tolyl)phosphine, tri(p-tolyl)phosphine,ethyldiphenylphosphine, dicyclohexylphenylphosphine,2-pyridyldiphenylphosphine, bis(6-methyl-2-pyridyl)phenylphosphine,tri(p-chlorophenyl)phosphine, tri(p-methoxyphenyl)phosphine,diphenyl(2-sulfonatophenyl)phosphine; potassium, sodium and ammoniumsalts of diphenyl(3-sulfonatophenyl)phosphine,bis(4,6-dimethyl-3-sulfonatophenyl)(2,4-dimethylphenyl)phosphine,bis(3-sulfonatophenyl)phenylphosphines,tris(4,6-dimethyl-3-sulfonatophenyl)phosphines,tris(2-sulfonatophenyl)phosphines, tris(3-sulfonatophenyl)phosphines;2-bis(diphenylphosphinoethyl)trimethylammonium iodide,2′-dicyclohexylphosphino-2,6-dimethoxy-3-sulfonato-1,1-biphenyl sodiumsalt, trimethyl phosphite and/or triphenyl phosphite.

The ligands more preferably comprise bidentate ligands of the generalformula

R¹¹M″-Z-M″ R¹¹   (VII).

In this formula, each M″ independently is N, P, As or Sb.

M″ is preferably the same in the two occurrences and more preferably isa phosphorus atom.

Each R¹¹ group independently represents the radicals described underformula (VI). The R¹¹ groups are preferably all identical.

Z is preferably a bivalent bridging group which contains at least 1bridging atom, preferably from 2 to 6 bridging atoms.

Bridging atoms can be selected from carbon, nitrogen, oxygen, siliconand sulfur atoms. Z is preferably an organic bridging group containingat least one carbon atom. Z is preferably an organic bridging groupcontaining 1 to 6 bridging atoms, of which at least two are carbonatoms, which may be substituted or unsubstituted.

Preferred Z groups are —CH₂—, —CH₂—CH₂—, —CH₂—CH₂—CH₂—,—CH₂—CH(CH₃)—CH₂—, —CH₂—C(CH₃)₂—CH₂—, —CH₂—C(C₂H₅)—CH₂—,—CH₂—Si(CH₃)₂—CH₂—, —CH₂—O—CH₂—, —CH₂—CH₂—CH₂—CH₂—, —CH₂—CH(C₂H₅)—CH₂—,—CH₂—CH(n-Pr)—CH and —CH₂—CH(n-Bu)-CH₂—, substituted or unsubstituted12-phenyl, 1,2-cyclohexyl, 1,1′- or 1,2-ferrocenyl radicals,2,2′-(1,1′-biphenyl), 4,5-xanthene and/or oxydi-2,1-phenylene radicals.

Examples of suitable bidentate phosphine ligands (VII) are for example1,2-bis(dimethylphosphino)ethane, 1,2-bis(diethylphosphino)ethane,1,2-bis(dipropylphosphino)ethane, 1,2-bis(diisopropylphosphino)ethane,1,2-bis(dibutylphosphino)ethane, 1,2-bis(di-tert-butylphosphino)ethane,1,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane;1,3-bis(dicyclohexylphosphino)propane,1,3-bis(diisopropylphosphino)propane,1,3-bis(di-tert-butylphosphino)propane,1,3-bis(diphenylphosphino)propane; 1,4-bis(diisopropylphosphino)butane,1,4-bis(diphenylphosphino)butane; 1,5-bis(dicyclohexylphosphino)pentane,1,2-bis(di-tert-butylphosphino)benzene,1,2-bis(diphenylphosphino)benzene,1,2-bis(dicyclohexylphosphino)benzene,1,2-bis(dicyclopentylphosphino)benzene,1,3-bis(di-tert-butylphosphino)benzene,1,3-bis(diphenylphosphino)benzene,1,3-bis(dicyclohexylphosphino)benzene,1,3-bis(dicyclopentylphosphino)benzene;9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene,9,9-dimethyl-4,5-bis(diphenylphosphino)-2,7-di-tert-butylxanthene,9,9-dimethyl-4,5-bis(di-tert-butylphosphino)xanthene,1,1′-bis(diphenylphosphino)ferrocene,2,2′-bis(diphenylphosphino)-1,1′-binaphthyl,2,2′-bis(di-p-tolyl-phosphino)-1,1′-binaphthyl,(oxydi-2,1-phenylene)bis(diphenylphosphine),2,5-(diisopropylphospholano)benzene,2,3-O-isopropropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane,2,2′-bis(di-tert-butylphosphino)-1,1′-biphenyl,2,2′-bis(dicyclohexylphosphino)-1,1′-biphenyl,2,2′-bis(diphenylphosphino)-1,1′-biphenyl,2-(di-tert-butylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(dicyclohexylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(diphenylphosphino)-2′-(N,N-dimethylamino)biphenyl,2-(diphenylphosphino)ethylamine, 2-[2-(diphenylphosphino)ethyl]pyridine;potassium, sodium and ammonium salts of1,2-bis(di-4-sulfonatophenylphosphino)benzene,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-4,4′,7,7′-tetrasulfonato-1,1′-binapthyl,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-5,5′-tetrasulfonato-1,1′-biphenyl,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-1,1′-binapthyl,(2,2′-bis[[bis(3-sulfonatophenyl)phosphino]methyl]-1,1′-biphenyl,9,9-dimethyl-4,5-bis(diphenylphosphino)-2,7-sulfonatoxanthene,9,9-dimethyl-4,5-bis(di-tert-butylphosphino)-2,7-sulfonatoxanthene,1,2-bis(di-4-sulfonatophenylphosphino)benzene,meso-tetrakis(4-sulfonatophenyl)porphine,meso-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphine,meso-tetrakis(3-sulfonatomesityl)porphine,tetrakis(4-carboxyphenyl)porphine and5,11,17,23-sulfonato-25,26,27,28-tetrahydroxy-calix[4]arene.

Moreover, the ligands of the formulae (VI) and (VII) can be attached toa suitable polymer or inorganic substrate by the R¹¹ radicals and/or thebridging group.

The molar transition metal/ligand ratio of the catalyst system is in therange 1:0.01 to 1:100, preferably in the range from 1:0.05 to 1:10 andmore preferably in the range from 1:1 to 1:4.

The reactions in the process stages a), b) and c) preferably take place,if desired, in an atmosphere comprising further gaseous constituentssuch as nitrogen, oxygen, argon, carbon dioxide for example; thetemperature is in the range from −20 to 340° C., more particularly inthe range from 20 to 180° C., and total pressure is in the range from 1to 100 bar.

The products and/or the transition metal and/or the transition metalcompound and/or catalyst system and/or the ligand and/or startingmaterials are optionally isolated after the process stages a), b) and c)by distillation or rectification, by crystallization or precipitation,by filtration or centrifugation, by adsorption or chromatography orother known methods.

According to the present invention, solvents, auxiliaries and any othervolatile constituents are removed by distillation, filtration and/orextraction for example.

The reactions in the process stages a), b) and c) are preferably carriedout, if desired, in absorption columns, spray towers, bubble columns,stirred tanks, trickle bed reactors, flow tubes, loop reactors and/orkneaders.

Suitable mixing elements include for example anchor, blade, MIG,propeller, impeller and turbine stirrers, cross beaters, disperserdisks, hollow (sparging) stirrers, rotor-stator mixers, static mixers,Venturi nozzles and/or mammoth pumps.

The intensity of mixing experienced by the reaction solutions/mixturespreferably corresponds to a rotation Reynolds number in the range from 1to 1 000 000 and preferably in the range from 100 to 100 000.

It is preferable for an intensive commixing of the respective reactantsetc. to be effected by an energy input in the range from 0.080 to 10kW/m³, preferably 0.30-1.65 kW/m³.

During the reaction, the particular catalyst A is preferably homogeneousand/or heterogeneous in action. Therefore, the particular heterogeneouscatalyst is effective during the reaction as a suspension or bound to asolid phase.

Preferably, the particular catalyst A is generated in situ before thereaction and/or at the start of the reaction and/or during the reaction.

Preferably, the particular reaction takes place in a solvent as asingle-phase system in homogeneous or heterogeneous mixture and/or inthe gas phase.

When a multi-phase system is used, a phase transfer catalyst may be usedin addition.

The reactions of the present invention can be carried out in liquidphase, in the gas phase or else in supercritical phase. The particularcatalyst A is preferably used in the case of liquids in homogeneous formor as a suspension, while a fixed bed arrangement is advantageous in thecase of gas phase or supercritical operation.

Suitable solvents are water, alcohols, e.g. methanol, ethanol,isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol, n-amylalcohol, isoamyl alcohol, tert-amyl alcohol, n-hexanol, n-octanol,isooctanol, n-tridecanol, benzyl alcohol, etc. Preference is furthergiven to glycols, e.g. ethylene glycol, 1,2-propanediol,1,3-propanediol, 1,3-butanediol, 1,4-butanediol, diethylene glycol etc.;aliphatic hydrocarbons, such as pentane, hexane, heptane, octane, andpetroleum ether, naphtha, kerosene, petroleum, paraffin oil, etc.;aromatic hydrocarbons, such as benzene, toluene, xylene, mesitylene,ethylbenzene, diethylbenzene, etc.; halogenated hydrocarbons, such asmethylene chloride, chloroform, 1,2-dichloro-ethane, chlorobenzene,carbon tetrachloride, tetrabromoethylene, etc.; alicyclic hydrocarbons,such as cyclopentane, cyclohexane, and methylcyclohexane, etc.; ethers,such as anisole (methyl phenyl ether), tert-butyl methyl ether, dibenzylether, diethyl ether, dioxane, diphenyl ether, methyl vinyl ether,tetrahydrofuran, triisopropyl ether etc.; glycol ethers, such asdiethylene glycol diethyl ether, diethylene glycol dimethyl ether(diglyme), diethylene glycol monobutyl ether, diethylene glycolmonomethyl ether, 1,2-dimethoxyethane (DME, monoglyme), ethylene glycolmonobutyl ether, triethylene glycol dimethyl ether (triglyme),triethylene glycol monomethyl ether etc.; ketones, such as acetone,diisobutyl ketone, methyl n-propyl ketone; methyl ethyl ketone, methylisobutyl ketone etc.; esters, such as methyl formate, methyl acetate,ethyl acetate, n-propyl acetate, and n-butyl acetate, etc.; carboxylicacids, such as formic acid, acetic acid, propionic acid, butyric acid,etc. One or more of these compounds can be used, alone or incombination.

Suitable solvents also encompass the phosphinic acid sources and olefinsused. These have advantages in the form of higher space-time yield.

It is preferable that the reaction be carried out under the autogenousvapor pressure of the olefin and/or of the solvent.

Preferably, R¹, R², R³ and R⁴ of olefin (IV) are the same or differentand each is independently H, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, tert-butyl and/or phenyl.

Preference is also given to using functionalized olefins such as allylisothiocyanate, allyl methacrylate, 2-allylphenol, N-allylthiourea,2-(allylthio)-2-thiazoline, allyltrimethylsillane, allyl acetate, allylacetoacetate, allyl alcohol, allylamine, allylbenzene, allyl cyanide,allyl cyanoacetate, allylanisole, trans-2-pentenal,cis-2-pentenenitrile, 1-penten-3-ol, 4-penten-1-ol, 4-penten-2-ol,trans-2-hexenal, trans-2-hexen-1-ol, cis-3-hexen-1-ol, 5-hexen-1-ol,styrene, -methylstyrene, 4-methylstyrene, vinyl acetate,9-vinylanthracene, 2-vinylpyridine, 4-vinylpyridine and1-vinyl-2-pyrrolidone.

The partial pressure of the olefin during the reaction is preferably0.01-100 bar and more preferably 0.1-10 bar.

The phosphinic acid/olefin molar ratio for the reaction is preferably inthe range from 1:10 000 to 1:0.001 and more preferably in the range from1:30 to 1:0.01.

The phosphinic acid/catalyst molar ratio for the reaction is preferablyin the range from 1:1 to 1:0.00000001 and more preferably in the rangefrom 1:0.01 to 1:0.000001.

The phosphinic acid/solvent molar ratio for the reaction is preferablyin the range from 1:10 000 to 1:0 and more preferably in the range from1:50 to 1:1.

One method the present invention provides for producing compounds of theformula (II) comprises reacting a phosphinic acid source with olefins inthe presence of a catalyst and freeing the product (II)(alkylphosphonous acid, salts or esters) of catalyst, transition metalor transition metal compound as the case may be, ligand, complexingagent, salts and by-products.

The present invention provides that the catalyst, the catalyst system,the transition metal and/or the transition metal compound are separatedoff by adding an auxiliary 1 and removing the catalyst, the catalystsystem, the transition metal and/or the transition metal compound byextraction and/or filtration.

The present invention provides that the ligand and/or complexing agentis separated off by extraction with auxiliary 2 and/or distillation withauxiliary 2.

Auxiliary 1 is preferably water and/or at least one member of the groupof metal scavengers. Preferred metal scavengers are metal oxides, suchas aluminum oxide, silicon dioxide, titanium dioxide, zirconium dioxide,zinc oxide, nickel oxide, vanadium oxide, chromium oxide, magnesiumoxide, Celite®, kieselguhr; metal carbonates, such as barium carbonate,calcium carbonate, strontium carbonate; metal sulfates, such as bariumsulfate, calcium sulfate, strontium sulfate; metal phosphates, such asaluminum phosphate, vanadium phosphate, metal carbides, such as siliconecarbide; metal aluminates, such as calcium aluminate; metal silicates,such as aluminum silicate, chalks, zeolites, bentonite, montmorillonite,hectorite; functionalized silicates, functionalized silica gels, such asSiliaBond®, QuadraSil™; functionalized polysiloxanes, such as Deloxan®;metal nitrides, carbon, activated carbon, mullite, bauxite, antimonite,scheelite, perovskite, hydrotalcite, functionalized and unfunctionalizedcellulose, chitosan, keratin, heteropolyanions, ion exchangers, such asAmberlite™, Amberjet™, Ambersep™, Dowex®, Lewatit®, ScavNet®;functionalized polymers, such as Chelex®, QuadraPure®, Smopex®,PolyOrgs®; polymer-bound phosphanes, phosphane oxides, phosphinates,phosphonates, phosphates, amines, ammonium salts, amides, thioamides,urea, thioureas, triazines, imidazoles, pyrazoles, pyridines,pyrimidines, pyrazines, thiols, thiol ethers, thiol esters, alcohols,alkoxides, ethers, esters, carboxylic acids, acetates, acetals,peptides, hetarenes, polyethyleneimine/silicon dioxide, and/ordendrimers.

It is preferable that the amounts added of auxiliary 1 correspond to0.1-40% by weight loading of the metal on auxiliary 1. It is preferablethat auxiliary 1 be used at temperatures of from 20 to 90° C. It ispreferable that the residence time of auxiliary 1 be from 0.5 to 360minutes.

Auxiliary 2 is preferably the aforementioned solvent of the presentinvention as are preferably used in process stage a).

The esterification of the monoamino-functionalized dialkylphosphinicacid (III) or of the alkylphosphonous acid derivatives (II) and also ofthe phosphinic acid source (I) to form the corresponding esters can beachieved for example by reaction with higher-boiling alcohols byremoving the resultant water by azeotropic distillation, or by reactionwith epoxides (alkylene oxides)

Preferably, following step a), the alkylphosphonous acid (II) isdirectly esterified with an alcohol of the general formula M-OH and/orM′-OH or by reaction with alkylene oxides, as indicated hereinbelow.

M-OH preferably comprises primary, secondary or tertiary alcohols havinga carbon chain length of C₁-C₁₈. Particular preference is given tomethanol, ethanol, propanol, isopropanol, n-butanol, 2-butanol,tert-butanol amyl alcohol and/or hexanol.

M′-OH preferably comprises ethylene glycol, 1,2-propylene glycol,1,3-propylene glycol, 1,4-butanediol, 2,2-dimethylpropane-1,3-diol,neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerol,trishydroxymethylethane, trishydroxymethylpropane, pentaerythritol,sorbitol, mannitol, a-naphthol, polyethylene glycols, polypropyleneglycols and/or EO-PO block polymers

Also useful as M-OH and M′-OH are mono- or polyhydric unsaturatedalcohols having a carbon chain length of C₁-C₁₈, for examplen-but-2-en-1-ol, 1,4-butenediol and allyl alcohol.

Also useful as M-OH and M′-OH are reaction products of monohydricalcohols with one or more molecules of alkylene oxides, preferably withethylene oxide and/or 1,2-propylene oxide. Preference is given to2-methoxyethanol, 2-ethoxyethanol, 2-n-butoxyethanol,2-(2′-ethylhexyloxy)ethanol, 2-n-dodecoxyethanol, methyl diglycol, ethyldiglycol, isopropyl diglycol, fatty alcohol polyglycol ethers and arylpolyglycol ethers.

M-OH and M′-OH are also preferably reaction products of polyhydricalcohols with one or more molecules of alkylene oxide, more particularlydiglycol and triglycol and also adducts, of 1 to 6 molecules of ethyleneoxide or propylene oxide onto glycerol, trishydroxymethylpropane orpentaerythritol.

Useful M-OH and M′-OH further include reaction products of water withone or more molecules of alkylene oxide. Preference is given topolyethylene glycols and poly-1,2-propylene glycols of various molecularsizes having an average molecular weight of 100-1000 g/mol and morepreferably of 150-350 g/mol.

Preference for use as M-OH and M′-OH is also given to reaction productsof ethylene oxide with poly-1,2-propylene glycols or fatty alcoholpropylene glycols; similarly reaction products of 1,2-propylene oxidewith polyethylene glycols or fatty alcohol ethoxylates. Preference isgiven to such reaction products with an average molecular weight of100-1000 g/mol, more preferably of 150-450 g/mol.

Also useful as M-OH and M′-OH are reaction products of alkylene oxideswith ammonia, primary or secondary amines, hydrogen sulfide, mercaptans,oxygen acids of phosphorus and C₂-C₆ dicarboxylic acids. Suitablereaction products of ethylene oxide with nitrogen compounds aretriethanolamine, methyldiethanolamine, n-butyldiethanolamine,n-dodecyldiethanolamine, dimethylethanolamine,n-butylmethylethanolamine, di-n-butylethanolamine,n-dodecylmethylethanolamine, tetrahydroxyethylethylenediamine orpentahydroxyethyldiethylenetriamine. Preferred alkylene oxides areethylene oxide, 1,2-propylene oxide, 1,2-epoxybutane,1,2-epoxyethylbenzene, (2,3-epoxypropyl)benzene, 2,3-epoxy-1-propanoland 3,4-epoxy-1-butene.

Suitable solvents are the solvents mentioned in process step a) and alsothe M-OH and M′-OH alcohols used and the alkylene oxides. These offeradvantages in the form of a higher space-time yield.

The reaction is preferably carried out under the autogenous vaporpressure of the employed alcohol M-OH, M′-OH and alkylene oxide and/orof the solvent.

Preferably, the reaction is carried out at a partial pressure of theemployed alcohol M-OH, M′-OH and alkylene oxide of 0.01-100 bar, morepreferably at a partial pressure of the alcohol of 0.1-10 bar.

The reaction is preferably carried out at a temperature in the rangefrom −20 to 340° C. and is more preferably carried out at a temperaturein the range from 20 to 180° C.

The reaction is preferably carried out at a total pressure in the rangefrom 1 to 100 bar.

The reaction is preferably carried out in a molar ratio for the alcoholor alkylene oxide component to the phosphinic acid source (I) oralkylphosphonous acid (II) or monoamino-functionalized dialkylphosphinicacid (III) ranging from 10 000:1 to 0.001:1 and more preferably from1000:1 to 0.01:1.

The reaction is preferably carried out in a molar ratio for thephosphinic acid source (I) or alkylphosphonous acid (II) ormonoamino-functionalized dialkylphosphinic acid (III) to the solventranging from 1:10 000 to 1:0 and more preferably in a phosphinicacid/solvent molar ratio ranging from 1:50 to 1:1.

Particularly preferred catalysts B as used in process stage b) areperoxo compounds such as peroxomonosulfuric acid, potassiummonopersulfate (potassium peroxomonosulfate), Caroat™, Oxone™,peroxodisulfuric acid, potassium persulfate (potassium peroxodisulfate),sodium persulfate (sodium peroxodisulfate), ammonium persulfate(ammonium peroxodisulfate).

Particularly preferred catalysts B are compounds capable of formingperoxides in the solvent system, such as sodium peroxide, sodiumperoxide hydrates, lithium peroxide, lithium peroxide hydrates, calciumperoxide, strontium peroxide, barium peroxide, magnesium peroxide, zincperoxide, potassium hyperoxide, potassium hyperoxide hydrates, sodiumperoxoborate, sodium peroxoborate hydrates, potassium peroxoborateperoxohydrate, magnesium peroxoborate, calcium peroxoborate, bariumperoxoborate, strontium peroxoborate, potassium peroxoborate,peroxomonophosphoric acid, peroxodiphosphoric acid, potassiumperoxodiphosphate, ammonium peroxodiphosphate, potassium ammoniumperoxodiphosphates (double salt), sodium carbonate peroxohydrate, ureaperoxohydrate, ammonium oxalate peroxide, barium peroxide peroxohydrate,barium peroxide peroxohydrate, calcium hydrogen peroxides, calciumperoxide peroxohydrate, ammonium triphosphate diperoxophosphate hydrate,potassium fluoride peroxohydrate, potassium fluoride triperoxohydrate,potassium fluoride diperoxohydrate, sodium pyrophosphatediperoxohydrate, sodium pyrophosphate diperoxohydrate octahydrate,potassium acetate peroxohydrate, sodium phosphate peroxohydrate, sodiumsilicate peroxohydrate.

Preferred catalysts B are hydrogen peroxide, performic acid, peraceticacid, benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide,2,4-dichlorobenzoyl peroxide, decanoyl peroxide, lauryl peroxide, cumenehydroperoxide, pinene hydroperoxide, p-menthane hydroperoxide, t-butylhydroperoxide, acetylacetone peroxide, methyl ethyl ketone peroxide,succinic acid peroxide, dicetyl peroxydicarbonate, t-butylperoxyacetate, t-butylperoxymaleic acid, t-butyl peroxybenzoate, acetylcyclohexylsulfonyl peroxide.

Preferred catalysts B are water-soluble azo compounds. Particularpreference is given to azo initiators such as VAZO® 522,2′-azobis(2,4-dimethylvaleronitrile), VAZO® 64(azobis(isobutyronitrile), AIBN), VAZO® 672,2′-azobis(2-methylbutyronitrile), VAZO® 881,1′-azobis(cyclohexane-1-carbonitrile), VAZO® 68 fromDupont-Biesteritz, V-702,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), V-652,2′-azobis(2,4-dimethylvaleronitrile), V-601 dimethyl2,2′-azobis(2-methylpropionate), V-592,2′-azobis(2-methylbutyronitrile), V-401,1¹-azobis(cyclohexane-1-carbonitrile), VF-0962,2′-azobis[N-(2-propenyl)-2-methylpropionamide], V-301-[(cyano-1-methylethyl)azo]formamide, VAm-1102,2′-azobis(N-butyl-2-methylpropionamide), VAm-1112,2′-azobis(N-cyclohexyl-2-methylpropionamide), VA-046B2,2′-azobis[2-(2-imidazolin-2-yl)propane disulfate dihydrate, VA-0572,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]tetrahydrate,VA-061 2,2′-azobis[2-(2-imidazolin-2-yl)propane], VA-0802,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide,VA-085 2,2′-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propionamide}, VA-0862,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] from WakoChemicals.

It is also possible to use azo initiators such2-tert-butylazo-2-cyanopropane, dimethyl azodiisobutyrate,azodiisobutyronitrile, 2-tert-butylazo-1-cyanocyclohexane,1-tert-amylazo-1-cyanocyclohexane. Preference is further given to alkylperketals such as 2,2-bis-(tert-butylperoxy)butane, ethyl3,3-bis(tert-butylperoxy)butyrate, 1,1-di(tert-butylperoxy)cyclohexane.

The catalyst B is preferably used in amounts of 0.05 to 5 mol % based onthe respective allylamines (V).

The catalyst B is preferably used in amounts of 0.001 to 10 mol %, basedon the phosphorus-containing compound.

Suitable solvents are those used above in process stage a).

The catalyst B is preferably metered in at a rate of 0.01 to 10 mol % ofcatalyst per hour, based on the phosphorus-containing compound.

The reaction of the alkylphosphonous acids (II) with the allylamine (V)is preferably carried out at a temperature of 0 to 250° C., morepreferably at 20 to 200° C. and more particularly at 50 to 150° C.

The atmosphere for the reaction with the allylamine (V) preferablyconsists of constituents of the solvent and allylamine (V) to an extentof 50% to 99.9% by weight, preferably 70-95%.

The reaction during the addition of allylamine (V) is preferably carriedout at a pressure of 1-20 bar.

In a further embodiment of the method, the product mixture obtainedafter process stage a) and/or b) is worked up.

The monoamino-functionalized dialkylphosphinic acid or salt (III) canthereafter be converted into further metal salts.

The metal compounds which are used in process stage c) preferablycomprise compounds of the metals Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn,Ce, Bi, Sr, Mn, Li, Na, K, more preferably Mg, Ca, Al, Ti, Zn, Sn, Ce,Fe.

Suitable solvents for process stage c) are those used above in processstage a).

The reaction of process stage c) is preferably carried out in an aqueousmedium.

Process stage c) preferably comprises reacting themonoamino-functionalized dialkylphosphinic acids, esters and/or alkalimetal salts (III) obtained after process stage b) with metal compoundsof Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to form themonoamino-functionalized dialkylphosphinic acid salts (III) of thesemetals.

The reaction is carried out in a molar ratio of monoamino-functionalizeddialkylphosphinic acid, ester or salt (III) to metal in the range from8:1 to 1:3 (for tetravalent metal ions or metals having a stabletetravalent oxidation state), from 6:1 to 1:3 (for trivalent metal ionsor metals having a stable trivalent oxidation state), from 4:1 to 1:3(for divalent metal ions or metals having a stable divalent oxidationstate) and from 3:1 to 1:4 (for monovalent metal ions or metals having astable monovalent oxidation state).

Preferably, monoamino-functionalized dialkylphosphinic acid, ester orsalt (III) obtained in process stage b) is converted into thecorresponding dialkylphosphinic acid and the latter is reacted inprocess stage c) with metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ceor Fe to form the monoamino-functionalized dialkylphosphinic acid salts(III) of these metals.

Preferably, monoamino-functionalized dialkylphosphinic acid/ester (III)obtained in process stage b) is converted to a dialkylphosphinic acidalkali metal salt and the latter is reacted in process stage c) withmetal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe to form themonoamino-functionalized dialkylphosphinic acid salts (III) of thesemetals.

The metal compounds of Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe for processstage c) preferably comprise metals, metal oxides, hydroxides, oxidehydroxides, borates, carbonates, hydroxocarbonates, hydroxocarbonatehydrates, mixed metal hydroxocarbonates, mixed metal hydroxocarbonatehydrates, phosphates, sulfates, sulfate hydrates, hydroxosulfatehydrates, mixed metal hydroxosulfate hydrates, oxysulfates, acetates,nitrates, fluorides, fluoride hydrates, chlorides, chloride hydrates,oxychlorides, bromides, iodides, iodide hydrates, carboxylic acidderivatives and/or alkoxides.

The metal compounds preferably comprise aluminum chloride, aluminumhydroxide, aluminum nitrate, aluminum sulfate, titanyl sulfate, zincnitrate, zinc oxide, zinc hydroxide and/or zinc sulfate.

Also suitable are aluminum metal, fluoride, hydroxychloride, bromide,iodide, sulfide, selenide; phosphide, hypophosphite, antimonide,nitride; carbide, hexafluorosilicate; hydride, calcium hydride,borohydride; chlorate; sodium aluminum sulfate, aluminum potassiumsulfate, aluminum ammonium sulfate, nitrate, metaphosphate, phosphate,silicate, magnesium silicate carbonate, hydrotalcite, sodium carbonate,borate, thiocyanate oxide, oxide hydroxide, their corresponding hydratesand/or polyaluminum hydroxy compounds, which preferably have an aluminumcontent of 9 to 40% by weight.

Also suitable are aluminum salts of mono-, di-, oligo-, polycarboxylicacids such as, for example, aluminum diacetate, acetotartrate, formate,lactate, oxalate, tartrate, oleate, palmitate, stearate,trifluoromethanesulfonate, benzoate, salicylate, 8-oxyquinolate.

Likewise suitable are elemental, metallic zinc and also zinc salts suchas for example zinc halides (zinc fluoride, zinc chlorides, zincbromide, zinc iodide).

Also suitable are zinc borate, carbonate, hydroxide carbonate, silicate,hexafluorosilicate, stannate, hydroxide stannate, magnesium aluminumhydroxide carbonate; nitrate, nitrite, phosphate, pyrophosphate;sulfate, phosphide, selenide, telluride and zinc salts of the oxoacidsof the seventh main group (hypohalites, halites, halates, for examplezinc iodate, perhalates, for example zinc perchlorate); zinc salts ofthe pseudohalides (zinc thiocyanate, zinc cyanate, zinc cyanide); zincoxides, peroxides, hydroxides or mixed zinc oxide hydroxides.

Preference is given to zinc salts of the oxoacids of transition metals(for example zinc chromate(VI) hydroxide, chromite, molybdate,permanganate, molybdate).

Also suitable are zinc salts of mono-, di-, oligo-, polycarboxylicacids, for example zinc formate, acetate, trifluoroacetate, propionate,butyrate, valerate, caprylate, oleate, stearate, oxalate, tartrate,citrate, benzoate, salicylate, lactate, acrylate, maleate, succinate,salts of amino acids (glycine), of acidic hydroxyl functions (zincphenoxide etc), zinc p-phenolsulfonate, acetylacetonate, stannate,dimethyldithiocarbamate, trifluoromethanesulfonate.

In the case of titanium compounds, metallic titanium is as istitanium(III) and/or (IV) chloride, nitrate, sulfate, formate, acetate,bromide, fluoride, oxychloride, oxysulfate, oxide, n-propoxide,n-butoxide, isopropoxide, ethoxide, 2-ethylhexyl oxide.

Also suitable is metallic tin and also tin salts (tin(II) and/or (IV)chloride); tin oxides and tin alkoxide such as, for example, tin(IV)tert-butoxide.

Cerium(III) fluoride, chloride and nitrate are also suitable.

In the case of zirconium compounds, metallic zirconium is preferred asare zirconium salts such as zirconium chloride, zirconium sulfate,zirconyl acetate, zirconyl chloride. Zirconium oxides and also zirconium(IV) tert-butoxide are also preferred.

The reaction in process stage c) is preferably carried out at a solidscontent of the monoamino-functionalized dialkylphosphinic acid salts inthe range from 0% to 70% by weight, preferably 5% to 40% by weight.

The reaction in process stage c) is preferably carried out at atemperature of 20 to 250° C., preferably at a temperature of 80 to 120°C.

The reaction in process stage c) is preferably carried out at a pressurebetween 0.01 and 1000 bar, preferably 0.1 to 100 bar.

The reaction in process stage c) preferably takes place during areaction time in the range from 1*10⁻⁷ to 1000 h.

Preferably, the monoamino-functionalized dialkylphosphinic acid salt(III) removed after process stage c) from the reaction mixture byfiltration and/or centrifugation is dried.

Preferably, the product mixture obtained after process stage b) isreacted with the metal compounds without further purification.

Preferred solvents are the solvents mentioned in process step a).

The reaction in process stage b) and/or c) is preferably carried out inthe solvent system given by stage a).

The reaction in process stage c) is preferred in a modified givensolvent system. Acidic components, solubilizers, foam inhibitors, etcare added for this purpose.

In a further embodiment of the method, the product mixture obtainedafter process stage a) and/or b) is worked up.

In a further embodiment of the method, the product mixture obtainedafter process stage b) is worked up and thereafter themonoamino-functionalized dialkylphosphinic acids and/or salts or esters(III) obtained after process stage b) are reacted in process stage c)with the metal compounds.

Preferably, the product mixture after process stage d) is worked up byisolating the monoamino-functionalized dialkylphosphinic acids and/orsalts or esters (III) by removing the solvent system, for example byevaporation.

Preferably, the monoamino-functionalized dialkylphosphinic acid salt(III) of the metals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe selectively hasa residual moisture content of 0.01% to 10% by weight, preferably of0.1% to 1% by weight,

an average particle size of 0.1 to 2000 μm, preferably of 10 to 500 μm,

a bulk density of 80 to 800 g/l, preferably 200 to 700 g/l,

and a Pfrengle flowability of 0.5 to 10, preferably of 1 to 5.

The amino functionality of the monoamino-functionalizeddialkylphosphinic acids, their salts and esters of the formula (III) canbe reacted thereafter with mineral acids, carboxylic acids, Lewis acids,organic acids or mixtures thereof to form further ammonium salts.

The reaction is preferably carried out at a temperature of 0 to 150° C.,particularly preferably at a temperature of 20 to 70° C.

Suitable solvents are those used above in process stage a).

Preferred mineral acids are for example hydrochloric acid, sulfuricacid, nitric acid or phosphoric acid, phosphonic acid, phosphinic acid.

Preferred carboxylic acids are for example formic acid, acetic acid,propionic acid, butyric acid, lactic acid, palmitic acid, stearic acid,malonic acid, maleic acid, fumaric acid, tartaric acid, citric acid andascorbic acid.

Preferred Lewis acids are boranes, for example diborane, trialkylborane,for example trimethylborane, triethylborane, tributylborane andtriarylborane, for example triphenylborane.

It is particularly preferable for the ammonium salts to comprise saltsof the abovementioned monoamino-functionalized dialkylphosphinic acids,their salts and esters with hydrochloric acid, phosphoric acid,phosphonic acid, phosphinic acid, acetic acid, citric acid, ascorbicacid, triphenylborane.

The molded articles, films, threads and fibers more preferably containfrom 5% to 30% by weight of the monoamino-functionalizeddialkylphosphinic acid/ester/salts produced according to one or more ofclaims 1 to 12, from 5% to 90% by weight of polymer or mixtures thereof,from 5% to 40% by weight of additives and from 5% to 40% by weight offiller, wherein the sum total of the components is always 100% byweight.

The additives preferably comprise antioxidants, antistats, blowingagents, further flame retardants, heat stabilizers, impact modifiers,processing aids, lubricants, light stabilizers, antidripping agents,compatibilizers, reinforcing agents, fillers, nucleus-forming agents,nucleating agents, additives for laser marking, hydrolysis stabilizers,chain extenders, color pigments, softeners, plasticizers and/orplasticizing agents.

Preference is given to a flame retardant containing 0.1 to 90% by weightof the low-halogen monoamino-functionalized dialkylphosphinic acid,ester and salts (III) and 0.1% to 50% by weight of further additives,more preferably dials.

Preferred additives are also aluminum trihydrate, antimony oxide,brominated aromatic or cycloaliphatic hydrocarbons, phenols, ethers,chloroparaffin, hexachlorocyclopentadiene adducts, red phosphorus,melamine derivatives, melamine cyanurates, ammonium polyphosphates andmagnesium hydroxide.

Preferred additives are also further flame retardants, more particularlysalts of dialkylphosphinic acids.

More particularly, the present invention provides for the use of thepresent invention monoamino-functionalized dialkylphosphinic acid,esters and salts (III) as flame retardants or as an intermediate in themanufacture of flame retardants for thermoplastic polymers such aspolyesters, polystyrene or polyamide and for thermoset polymers such asunsaturated polyester resins, epoxy resins, polyurethanes or acrylates.

Suitable polyesters are derived from dicarboxylic acids and their estersand diols and/or from hydroxycarboxylic acids or the correspondinglactones.

It is particularly preferable to use terephthalic acid and ethyleneglycol, 1,3-propanediol, 1,3-butanediol.

Suitable polyesters include inter alia polyethylene terephthalate,polybutylene terephthalate (Celanex® 2500, Celanex® 2002, from Celanese;Ultradur®, from BASF), poly-1,4-dimethylolcyclohexane terephthalate,polyhydroxybenzoates, and also block polyether esters derived frompolyethers having hydroxyl end groups; and also polyesters modified withpolycarbonates or MBS.

The following steps can be carried out with or by addition of thecompounds produced according to the present invention.

Preferably, the molding material is produced from the free dicarboxylicacid and diols by initially esterifying directly and thenpolycondensing.

When proceeding from dicarboxylic esters, more particularly dimethylesters, it is preferable to first transesterify and then to polycondenseby using catalysts customary for this purpose.

Polyester production may preferably proceed by adding customaryadditives (crosslinking agents, matting agents and stabilizing agents,nucleating agents, dyes and fillers, etc) in addition to the customarycatalysts.

The esterification and/or transesterification involved in polyesterproduction is preferably carried out at temperatures of 100-300° C.,more preferably 150-250° C.

The polycondensation involved in polyester production preferably takesplace at pressures between 0.1 to 1.5 mbar and temperatures of 150-450°C., more preferably at 200-300° C.

The flame-retardant polyester molding materials produced according tothe present invention are preferably used in polyester molded articles.

Preferred polyester molded articles are threads, fibers, self-supportingfilms/sheets and molded articles containing mainly terephthalic acid asdicarboxylic acid component and mainly ethylene glycol as diolcomponent.

The resulting phosphorus content in threads and fibers produced fromflame-retardant polyesters is preferably 0.1%-18% by weight, morepreferably 0.5%-15% by weight and in the case of self-supportingfilms/sheets 0.2%-15% by weight, preferably 0.9%-12% by weight.

Suitable polystyrenes are polystyrene, poly(p-methylstyrene) and/orpoly(alpha-methylstyrene).

Suitable polystyrenes preferably comprise copolymers of styrene oralpha-methylstyrene with dienes or acrylic derivatives, for examplestyrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate,styrene-butadiene-alkyl acrylate and styrene-butadiene-alkylmethacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methylacrylate; mixtures of high impact strength from styrene copolymers andanother polymer, for example a polyacrylate, a diene polymer or anethylene-propylene-diene terpolymer; also block copolymers of styrene,for example styrene-butadiene-styrene, styrene-isoprene-styrenestyrene-ethylene/butylene-styrene or styrene-ethylene/propylene-styrene.

Suitable polystyrenes preferably also comprise graft copolymers ofstyrene or alpha-methylstyrene, for example styrene on polybutadiene,styrene on polybutadiene-styrene or polybutadiene-acrylonitrilecopolymers, styrene and acrylonitrile (or methacrylonitrile) onpolybutadiene; styrene, acrylonitrile and methyl methacrylate onpolybutadiene; styrene and maleic anhydride on polybutadiene; styrene,acrylonitrile and maleic anhydride or maleimide on polybutadiene;styrene and maleimide on polybutadiene, styrene and alkyl acrylates oralkyl methacrylates on polybutadiene, styrene and acrylonitrile onethylene-propylene-diene terpolymers, styrene and acrylonitrile onpoly(alkyl acrylate)s or poly(alkyl methacrylate)s, styrene andacrylonitrile on acrylate-butadiene copolymers, and also their mixtures,as are also known for example as ABS, MBS, ASA or AES polymers.

The polymers preferably comprise polyamides and copolyamides derivedfrom diamines and dicarboxylic acids and/or from aminocarboxylic acidsor the corresponding lactams, such as nylon-2,12, nylon-4, nylon-4,6,nylon-6, nylon-6,6, nylon-6,9, nylon-6,10, nylon-6,12, nylon-6,66,nylon-7,7, nylon-8,8, nylon-9,9, nylon-10,9, nylon-10,10, nylon-11,nylon-12, and so on. Such polyamides are known for example under thetrade names Nylon®, from DuPont, Ultramid®, from BASF, Akulon® K122,from DSM, Zytel® 7301, from DuPont; Durethan® B 29, from Bayer andGrillamid®, from Ems Chemie.

Also suitable are aromatic polyamides proceeding from m-xylene, diamineand adipic acid; polyamides produced from hexamethylenediamine and iso-and/or terephthalic acid and optionally an elastomer as modifier, forexample poly-2,4,4-trimethylhexamethyleneterephthalamide orpoly-m-phenyleneisophthalamide, block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers or with polyethers, for example withpolyethylene glycol, polypropylene glycol or polytetramethylene glycol.Also EPDM- or ABS-modified polyamides or copolyamides; and alsopolyamides condensed during processing (“RIM polyamide systems”).

The monoamino-functionalized dialkylphosphinic acid/ester/salts producedaccording to one or more of claims 1 to 11 are preferably used inmolding materials further used for producing polymeric molded articles.

It is particularly preferable for the flame-retardant molding materialto contain from 5% to 30% by weight of monoamino-functionalizeddialkylphosphinic acids, salts or esters produced according to one ormore of claims 1 to 11, from 5% to 90% by weight of polymer or mixturesthereof, from 5% to 40% by weight of additives and 5% to 40% by weightof filler, wherein the sum total of the components is always 100% byweight.

The present invention also provides flame retardants containingmonoamino-functionalized dialkylphosphinic acids, salts or estersproduced according to one or more of claims 1 to 11.

The present invention also provides polymeric molding materials and alsopolymeric molded articles, films, threads and fibers containingmonoamino-functionalized dialkylphosphinic acid salts (III) of themetals Mg, Ca, Al, Zn, Ti, Sn, Zr, Ce or Fe produced according to thepresent invention.

The examples which follow illustrate the invention.

Production, processing and testing of flame-retardant polymeric moldingmaterials and flame-retardant polymeric molded articles.

The flame-retardant components are mixed with the polymeric pellets andany additives and incorporated on a twin-screw extruder (Leistritz LSM®30/34) at temperatures of 230 to 260° C. (glassfiber-reinforced PBT) orof 260 to 280° C. (glassfiber-reinforced PA 66). The homogenizedpolymeric strand was hauled off, water bath cooled and then pelletized.

After sufficient drying, the molding materials were processed on aninjection molding machine (Aarburg Allrounder) at melt temperatures of240 to 270° C. (glassfiber-reinforced PBT) or of 260 to 290° C.(glassfiber-reinforced PA 66) to give test specimens. The test specimensare subsequently flammability tested and classified using the UL 94(Underwriter Laboratories) test.

UL 94 (Underwriter Laboratories) fire classification was determined ontest specimens from each mixture, using test specimens 1.5 mm inthickness.

The UL 94 fire classifications are as follows:

V-0: Afterflame time never longer than 10 sec, total of afterflame timesfor 10 flame applications not more than 50 sec, no flaming drops, nocomplete consumption of the specimen, afterglow time for specimens neverlonger than 30 sec after end of flame application.

V-1: Afterflame time never longer than 30 sec after end of flameapplication, total of afterflame time for 10 flame applications not morethan 250 sec, afterglow time for specimens never longer than 60 secafter end of flame application, other criteria as for V-0

V-2: Cotton indicator ignited by flaming drops, other criteria as forV-1

Not classifiable (ncl): does not comply with fire classification V-2.

Some investigated specimens were also tested for their LOI value. TheLOI (Limiting Oxygen Index) value is determined according to ISO 4589.According to ISO 4589, the LOI is the lowest oxygen concentration involume percent which in a mixture of oxygen and nitrogen will supportcombustion of the plastic. The higher the LOI value, the greater theflammability resistance of the material tested.

LOI   23 flammable LOI 24-28 potentially flammable LOI 29-35 flameresistant LOI >36 particularly flame-resistant

Chemicals and Abbreviations Used

-   -   VE water completely ion-free water    -   AIBN azobis(isobutyronitrile), (from WAKO Chemicals GmbH)    -   THF tetrahydrofuran    -   WakoV65 2,2′-azobis(2,4-dimethylvaleronitrile), (from WAKO        Chemicals GmbH)    -   Deloxan® THP II metal scavenger (from Evonik Industries AG)

EXAMPLE 1

At room temperature, a three-neck flask equipped with stirrer andhigh-performance condenser is initially charged with 188 g of water andthis initial charge is devolatilized by stirring and passing nitrogenthrough it. Then, under nitrogen, 0.2 mg of palladium(II) sulfate and2.3 mg of tris(3-sulfophenyl)phosphine trisodium salt are added, themixture is stirred, and then 66 g of phosphinic acid in 66 g of waterare added. The reaction solution is transferred to a 2 l Büchi reactorand charged with ethylene under superatmospheric pressure while stirringand the reaction mixture is heated to 80° C. After 28 g of ethylene hasbeen taken up, the system is cooled down and free ethylene isdischarged. The reaction mixture is freed of solvent on a rotaryevaporator. The residue is admixed with 100 g of VE water and at roomtemperature stirred under nitrogen, then filtered and the filtrate isextracted with toluene, thereafter freed of solvent on a rotaryevaporator and 92 g (98% of theory) of ethyiphosphonous acid arecollected.

EXAMPLE 2

Example 1 is repeated with 99 g of phosphinic acid, 396 g of butanol, 42g of ethylene, 6.9 mg of tris(dibenzylideneacetone)dipalladium, 9.5 mgof 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, followed bypurification over a column charged with Deloxan® THP II and the furtheraddition of n-butanol. At a reaction temperature of 80-110° C., thewater formed is removed by azeotropic distillation. The product ispurified by distillation at reduced pressure. Yield: 189 g (84% oftheory) of butyl ethylphosphonite.

EXAMPLE 3

Example 1 is repeated with 198 g of phosphinic acid, 198 g of water, 84g of ethylene, 6.1 mg of palladium(II) sulfate, 25.8 mg of9,9-dimethyl-4,5-bis(diphenylphosphino)-2,7-sulfonatoxanthene disodiumsalt, followed by purification over a column charged with Deloxan® THPII and the further addition of n-butanol. At a reaction temperature of80-110° C., the water formed is removed by azeotropic distillation. Theproduct is purified by distillation at reduced pressure. Yield: 374 g(83% of theory) of butyl ethylphosphonite.

EXAMPLE 4

A 500 ml five-neck flask equipped with gas inlet tube, thermometer,high-performance stirrer and reflux condenser with gas incineration ischarged with 94 g (1 mol) of ethylphosphonous acid (produced as inExample 1). Ethylene oxide is introduced at room temperature. A reactiontemperature of 70° C. is set with cooling, followed by further reactionat 80° C. for one hour. The ethylene oxide takeup is 65.7 g. The acidnumber of the product is less than 1 mg KOH/g. Yield: 129 g (94% oftheory) of 2-hydroxyethyl ethylphosphonite as colorless, water-clearproduct.

EXAMPLE 5

564 g (6 mol) of ethylphosphonous acid (produced as in Example 1) aredissolved in 860 g of water and initially charged to a 5 l five-neckflask equipped with thermometer, reflux condenser, high-performancestirrer and dropping funnel. The reaction mixture is heated to 100° C.and 654.5 g (7 mol) of allylamine hydrochloride and 500 g of a 5% sodiumperoxodisulfate solution (1.5 mol % based on allylamine hydrochloride)is added dropwise at atmospheric pressure over 1 h. Then, the reactionmixture is neutralized with about 560 g (7 mol) of 50% sodium hydroxidesolution and the water is distilled off in vacuo. The residue is takenup in tetrahydrofuran and extracted. The insoluble salts are filteredoff. The solvent of the filtrate is removed in vacuo. Yield: 752 g (83%of theory) of ethyl(3-aminopropyl)phosphinic acid as colorless solid.

EXAMPLE 6

150 g (1 mol) of butyl ethylphosphonite (produced as in Example 2) and68.4 g (1.2 mol) of allylamine are initially charged in 200 ml ofbutanol in a four-neck round-bottom flask equipped with stirrer, refluxcondenser, thermometer and nitrogen inlet, and heated. At about 100° C.,in the course of 1 h, 98.4 g of a 5% solution of AIBN in butanol areadded dropwise, whereafter the solvent is distilled off in vacuo.Chromatographic purification yields 135 g (65% of theory) of butylethyl(3-aminopropyl)phosphinate.

EXAMPLE 7

414 g (2 mol) of butyl ethyl(3-aminopropyl)phosphinate (produced as inExample 6) are initially charged to a 1 l five-neck flask equipped withthermometer, reflux condenser, high-performance stirrer and droppingfunnel. At 160° C., during 4 h, 500 ml of water are metered in and abutanol-water mixture is distilled off. The solid residue isrecrystallized from acetone to obtain 296 g (98% of theory) ofethyl(3-aminopropyl)phosphinic acid as colorless solid.

EXAMPLE 8

To 414 g (2 mol) of butyl ethyl(3-aminopropyl)phosphinate (produced asin Example 6) are added 155 g (2.5 mol) of ethylene glycol and 0.4 g ofpotassium titanyl oxalate followed by stirring at 200° C. for 2 h.Volatiles are distilled off by gradual evacuating to leave 374 g (96% oftheory) of 2-hydroxyethyl ethyl(3-aminopropyl)phosphinate.

EXAMPLE 9

906 g (6 mol) of ethyl(3-aminopropyl)phosphinic acid (produced as inExample 5) are dissolved in 860 g of water and initially charged in a 5l five-neck flask equipped with thermometer, reflux condenser,high-performance stirrer and dropping funnel and neutralized with about480 g (6 mol) of 50% sodium hydroxide solution. At 85° C., a mixture of1291 g of a 46% aqueous solution of Al₂(SO₄)₃.14 H₂O is added. The solidobtained is then filtered off, washed with hot water and dried at 130°C. under reduced pressure. Yield: 887 g (93% of theory) ofethyl-3-aminopropylphosphinic acid aluminum(III) salt as colorless salt.

EXAMPLE 10

165 g (1 mol) of ethyl(2-methyl-3-aminopropyl)phosphinic acid (producedsimilarly to Example 5) and 85 g of titanium tetrabutoxide are refluxedin 500 ml of toluene for 40 hours. The butanol formed is distilled offfrom time to time with fractions of toluene, and the resulting solutionis freed of solvent. Yield: 172 g (98% of theory) ofethyl(2-methyl-3-aminopropyl)phosphinic acid titanium salt.

EXAMPLE 11

165 g (1 mol) of ethyl(2-methyl-3-aminopropyl)phosphinic acid (producedsimilarly to Example 5) and 100 g of concentrated hydrochloric acid arestirred at room temperature for 1 hour. Water is distilled at reducedpressure to obtain 201 g (100% of theory) ofethyl(2-methyl-3-aminopropyl)phosphinic acid hydrochloride.

EXAMPLE 12

207 g (1 mol) of butyl ethyl(3-aminopropyl)phosphinate (produced as inExample 6) and 242 g (1 mol) of triphenylborane are stirred in 400 ml oftoluene at room temperature for 1 hour. The toluene is distilled off atreduced pressure to leave 449 g (100% of theory) of butylethyl(3-aminopropyl)phosphinate as triphenylborane adduct.

EXAMPLE 13

159 g (1 mol) of ethyl-3-aminopropylphosphinic acid aluminum(III) salt(produced as in Example 9) are stirred in 100 ml of acetic acid at roomtemperature for 1 hour. Excess acetic acid is distilled at reducedpressure to leave 219 g (100% of theory) ofethyl-3-aminopropylphosphinic acid aluminum(III) salt as acetic acidsalt.

EXAMPLE 14

A mixture of 50% by weight of polybutylene terephthalate, 20% by weightof ethyl(3-aminopropyl)phosphinic acid aluminum(III) salt (produced asin Example 9) and 30% by weight of glass fibers are compounded on atwin-screw extruder (Leistritz LSM 30/34) at temperatures of 230 to 260°C. to form a polymeric molding material. The homogenized polymericstrand was hauled off, water bath cooled and then pelletized. Afterdrying, the molding materials are processed on an injection moldingmachine (Aarburg Allrounder) at 240 to 270° C. to form polymeric moldedarticles which achieved a UL-94 classification of V-0.

EXAMPLE 15

A mixture of 53% by weight of nylon-6,6, 30% by weight of glass fibers,17% by weight of ethyl(2-methyl-3-aminopropyl)phosphinic acid titaniumsalt (produced as in Example 10) are compounded on a twin-screw extruder(Leistritz LSM 30/34) to form polymeric molding materials. Thehomogenized polymeric strand was hauled off, water bath cooled and thenpelletized. After drying, the molding materials are processed on aninjection molding machine (Aarburg Allrounder) at 260 to 290° C. to formpolymeric molded articles which achieved a UL-94 classification of V-0.

EXAMPLE 16

A 75% suspension of 15.1 g of ethyl(3-aminopropyl)phosphinic acid(produced as in Example 5) and 372.4 g of adipic acidhexamethylenediamine salt in water are initially charged to, andgradually raised to a temperature and pressure of 220° C. and 20 bar in,a steel autoclave under nitrogen. The temperature is subsequently raisedstepwise to about 240° C. and about 270° C. while maintaining thepressure, water formed is continuously removed from the autoclave, andthe pressure is gradually reduced to atmospheric. The polymer (335 g)contains 0.9% of phosphorus, the LOI is 32 and that of untreatednylon-6,6 is 24.

1. A method for producing monoamino-functionalized dialkylphosphinicacids, esters or salts, comprising the steps of: a) reacting aphosphinic acid source (I)

with one or more olefins (IV)

in the presence of a catalyst A to form an alkylphosphonous acid, saltor ester (II)

b) reacting the alkylphosphonous acid, salt or ester (II) with an atleast one allyl-amine (V)

in the presence of a catalyst B to form a monoamino-functionalizeddialkylphosphinic acid derivative (III)

where R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ are identical or different andare each independently H, C₁-C₁₈-alkyl, C₆-C₁₈-aryl, C₆-C₁₈-aralkyl,C₆-C₁₈-alkylaryl, CN, CHO, OC(O)CH₂CN, CH(OH)C₂H₅, CH₂CH(OH)CH₃,9-anthracene, 2-pyrrolidone, (CH₂)_(m)OH, (CH₂)_(m)NH₂, (CH₂)_(m)NCS,(CH₂)_(m)NC(S)NH₂, (CH₂)_(m)SH, (CH₂)_(m)S-2-thiazoline, (CH₂)_(m)SiMe₃,C(O)R¹⁰, (CH₂)_(m)C(O)R¹⁰, CH═CHR¹⁰ or CH═CH—C(O)R¹⁰ and where R¹⁰ isC₁-C₈-alkyl or C₆-C₁₈-aryl and m is an integer from 0 to 10 and X isC₁-C₁₈-alkyl, C₆-C₁₈-aryl, C₆-C₁₈-aralkyl, C₆-C₁₈-alkylaryl,(CH₂)_(k)OH, CH₂—CHOH—CH₂OH, (CH₂)_(k)O(CH₂)_(k)H,(CH₂)_(k)—CH(OH)—(CH₂)_(k)H, (CH₂—CH₂O)_(k)H, (CH₂—C[CH₃]HO)_(k)H,(CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)H, (CH₂—CH₂O)_(k)(CH₂—C[CH₃]HO)H,(CH₂—CH₂O)_(k)-alkyl, (CH₂—C[CH₃]HO)_(k)-alkyl,(CH₂—C[CH₃]HO)_(k)(CH₂—CH₂O)_(k)-alkyl,(CH₂—CH₂O)_(k)(CH₂—CH₃]HO)O-alkyl, (CH₂)_(k)—CH═CH(CH₂)_(k)H,(CH₂)_(k)NH₂ or (CH₂)_(k)N[(CH₂)_(k)H]₂, where k is an integer from 0 to10, Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Cu, Ni, Li,Na, K, H, a protonated nitrogen base and is a mineral acid, carboxylicacid, Lewis acid or organic acid or a combination thereof, where n is awhole or fractional number from 0 to 4 and the catalyst A is selectedfrom the group of transition metals, transition metal compounds,catalyst systems composed of a transition metal, transition metalcompound and at least one ligand and a combination thereof, and thecatalyst B is selected from the group consisting of peroxide-formingcompounds, peroxo compounds, azo compounds and a combination thereof. 2.The method according to claim 1 wherein the monoamino-functionalizeddialkylphosphinic acid, its salt or ester (III) obtained after step b)is reacted in a step d) with metal compounds of Mg, Ca, Al, Sb, Sn, Ge,Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K, a protonated nitrogen base ora combination thereof to form the monoamino-functionalizeddialkylphosphinic acid salts (III) of these metals, of a nitrogencompound or a combination thereof.
 3. The method according to claim 1wherein the alkylphosphonous acid, salt or ester (II) obtained afterstep a), the monoamino-functionalized dialkylphosphinic acid, salt orester (III) obtained after step b), the reaction solution thereof or acombination thereof are esterified with an alkylene oxide or an alcoholM-OH, M′-OH or a combination thereof, and the alkylphosphonous ester(II), monoamino-functionalized dialkylphosphinic ester (III) or acombination thereof are subjected to the reaction steps b) or c).
 4. Themethod according to claim 1, wherein the groups C₆-C₁₈-aryl,C₆-C₁₈-aralkyl and C₆-C₁₈-alkylaryl are substituted with SO₃X₂,—C(O)CH₃, OH, CH₂OH, CH₃SO₃X₂, PO₃X₂, NH₂, NO₂, OCH₃, SH, OC(O)CH₃ or acombination thereof.
 5. The method according to claim 1, wherein R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹ are identical or different and are eachindependently H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl or phenyl.
 6. The method according to claim 1, wherein X isH, Ca, Mg, Al, Zn, Ti, Fe, Ce, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, tert-butyl, phenyl, ethylene glycol, propyl glycol,butyl glycol, pentyl glycol, hexyl glycol, allyl, glycerol or acombination thereof.
 7. The method according to claim 1, wherein thetransition metals, transition metal compounds or a combination thereofare from the seventh or eighth transition groups.
 8. The methodaccording to claim 1, wherein the transition metals transition metalcompounds or a combination thereof are rhodium, nickel, palladium,platinum, ruthenium or a combination thereof.
 9. The method according toclaim 1, wherein the catalyst B is hydrogen peroxide, sodium peroxide,lithium peroxide, potassium persulfate, sodium persulfate, ammoniumpersulfate, sodium peroxodisulfate, potassium peroxoborate, peraceticacid, benzoyl peroxide, di-t-butyl peroxide, peroxodisulfuric acid,azobisisobutyronitrile, 2,2′-azobis(2-amidinopropane)dihydrochloride,2,2′-azobis(N,N′dimethyleneisobutyramidine)dihydrochloride or acombination thereof.
 10. The method according to claim 1, wherein theone or more allylamine (V) is allylamine, N-methylallylamine,N,N-dimethylallylamine, N-(trimethylsilyl)allylamine, N-allylaniline,N-methyl-N-allylaniline, N-methylallylaniline, 1,1-dimethylallylamine,2-methylallylamine, 3-phenylallylamine, allylcyclohexylamine,diallylamine, diallylmethylamine, triallylamine, their salts withmineral acids, carboxylic acids, Lewis acids, organic acids or mixturesthereof.
 11. The method according to claim 1, wherein the alcohol of thegeneral formula M-OH is a linear or branched, saturated or unsaturated,monohydric organic alcohol having a carbon chain length of C₁-C₁₈ andthe alcohol of the general formula M′-OH is a linear or branched,saturated or unsaturated polyhydric organic alcohol having a carbonchain length of C₁-C₁₈.
 12. A composition comprising amonoamino-functionalized dialkylphosphinic acid, ester or salt accordingto claim 1, wherein the composition is an intermediate for furthersyntheses, a binder, as a crosslinker to cure epoxy resins,polyurethanes and unsaturated polyester resins, an accelerant to cureepoxy resins, polyurethanes and unsaturated polyester resins, a polymerstabilizer, a crop protection agent, a therapeutic or additive intherapeutics for humans and animals, a sequestrant, as a mineral oiladditive, a corrosion control agent, a washing application, a cleaningapplication or an electronic application.
 13. A composition comprising amonoamino-functionalized dialkylphosphinic acid, ester or salt accordingto claim 1, wherein the composition is a flame retardant, a flameretardant for clearcoats and intumescent coatings, as a flame retardantfor wood and other cellulosic products, as a reactive flame retardantfor polymers, nonreactive flame retardant for polymers, aflame-retardant polymeric molding material, a flame-retardant polymericmolded article or a flame-retardant finishing of polyester and cellulosestraight and blend fabrics by impregnation.
 14. A flame-retardantthermoplastic or thermoset polymeric molding material containing 0.5% to45% by weight of a monoamino-functionalized dialkylphosphinic acid, saltor ester according to claim 1, 0.5% to 95% by weight of a thermoplasticor thermoset polymer or mixtures thereof, 0% to 55% by weight ofadditives and 0% to 55% by weight of filler or einforc ng materials,wherein the sum total of the components is 100% by weight. 15.Flame-retardant thermoplastic or thermoset polymeric molded articles,films, threads or fibers containing 0.5% to 45% by weight of amonoamino-functionalized dialkylphosphinic acid, salt or ester accordingto claim 1, 0.5% to 95% by weight of a thermoplastic or thermosetpolymer or mixtures thereof, 0% to 55% by weight of additives and 0% to55% by weight of filler or reinforcing materials, wherein the sum totalof the components is 100% by weight.